Modification of cellulose with butadiene diepoxide using a dioxane-water solvent system



United States Patent MODIFICATION OF CELLULOSE WITH BUTADI- ENE DIEPOXIDE USING A DIOXANE-WATER SOLVENT SYSTEM John B. McKelvey, Ralph J. Berni, and Ruth R. Benerito, New Orleans, 1.21., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Nov. 8, 1963, Ser. No. 322,556

7 Claims. (Cl. 8120) A nonexclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to the catalytic preparation of cellulosic others with butadienediepoxides.

The primary object of this invention is to cause reaction of butadienediepoxides with cotton collulose and/0r cellulosic derivatives such as viscose rayon, ramie, dialdehyde cotton, partially acetylated cotton, and carboxymethylated cotton, in such fashion that resiliency is developed in the fibers so that a fabric prepared by the process of this invention is substantially wrinkle-free when compressed and released in the dry state.

Resilience, as viewed here, is the ability to recover from deformation, and particularly as it applies to a quality or property of fabrics. Whether or not a given chemically treated cellulosic material exhibits this property can best be evaluated by one of the several available physical tests commonly employed in textile testing laboratories. The inventor here chose the Monsanto Wrinkle Recovery Test, which measures the crease angle of fabrics, as a criterion for measurement of resiliency imparted to the treated fabrics. The test is fully described in the text of American Society for Testing & Materials Designation D1295-60T.

The Monsanto conditioned wrinkle recovery angle should be at least 250 (Warp plus Filling) before it can be said to be resilient to the lowest acceptable degree. By process of this invention a very low degree of substitution is all that is needed to impart satisfactory resiliency to the fabrics, the order of substitution being in the order of a few hundreds of a BS. (degree of substitution).

The prior art established by Condo and Schroeder in US. Patent 2,752,269, discloses the application of diand polyepoxide compounds to cellulosic textiles, which reaction is catalyzed by compounds such as zinc fluoborate or cadmium fluoborate, with curing temperatures of 150 to 175 C.

The present invention discloses the use of other fluoborates and BF adducts, which includes boron trifiuoride complex of acetamide, the boron trifluoride complex of aniline and ammonia, fluoroboric acid, phenyldiazonium fluoborate, ammonium hexafluophosphate, phenyl phosphoniurn fluoborate, trimethylamine oxide-BF adduct, and other such type acid catalysts, in the catalyzing phase of the process.

In confirming the data contained in the Condo and Schroeder patent it was observed that the butadienediepoxides were either not added to cotton or were added in such small quantities-a few tenths of 1%-that the resiliency of the original fabric was essentially unchanged.

Furthermore, whereas the prior art deals with aqueous diepoxide-catalyst systems, the present invention deals with nonaqueous systems, in particular solutions of the diepoxide in the lower aliphatic alcohols, acetone, dioxane, and the like.

By the process of the present invention resiliency can be imparted to cotton and other cellulosic textiles at much lower temperatures than those disclosed by Schroder and Condo in either their paper (Textile Research Journal, 27, 135 (1957)) or their patent (US. Patent 2,752,269).

3,382,030 Patented May 7, 1968 While the process of the present invention employs temperatures about from 85 to 125 C. for an oven cure of 3 to 5 minutes, the prior art employs temperatures in the neighborhood of 160 to 190 C.

By process of the present invention a highly resilient fabric with a 0.7 to 1.8% weight gain can be obtained. This fabric shows no yellowing upon curing, has an increase in luster, suffers no scorching or yellowing upon ironing, and has minimum losses in tensile strength.

Although any of the butadienediepoxides (meso, a, l, or dl) react equally Well with cotton .and other cellulosic textiles in the present process, and yield equally satisfying results in that the finished fabrics are equal in every respect, the dl (racemic) mixture is preferred simply because of its commercial availability at this time.

The examples were prepared from select investigative data gained as the product of experimentation.

EXAMPLE 1 A catalytic reaction solution having the following composition was prepared:

Ingredient: Parts by Weight al Butadienediepoxide (B.P. 145 C.) 10.0 Zinc fluoborate (40% aqueous) solution 1.5 Methanol 88.5

This solution was applied to 80 x 80 cotton fabric using a conventional padder. The fabric was then passed through squeeze rolls adjusted to give a wet pickup of 80%. The fabric was immediately hung to dry and cure in a draft oven for 5 minutes at 125 C. The final weight gain after the usual washing and air drying was 1.8% (0.034 D.S.).

The resiliency was evaluated employing Monsanto Wrinkle Recovery Test (ASTM D1295-60T) values as suitable criterion. The untreated cotton is here considered as the control fabric. The crease angle, or wrinkle recovery, value of the control fabric was 195, warp plus filling (Vt 81F). The treated fabric value was 280, and increase of 43%.

A second cotton fabric sample was treated, duplicating the above procedure with but one variation, water was employed where methanol had been used as solvent, and a wet gain of 95% was obtained. The treatment in the aqueous system yielded a fabric with apparently no change in properties, no gain in weight, and substantially no change in crease angle value. The finished second fabric sample had a crease angle value of only 193 EXAMPLE 2 The meso-butadienediepoxide (B.P. 138 C.) was used in the same manner as the dl form was in Example 1,

using methanol as solvent, and a wet pickup of 85% was obtained. Analysis of the finished fabric shows a crease angle (dry) value of 280 (W&F) at a weight gain of 1.7% (0.032 D.S.). A similar experiment with a wet pickup, had yielded a fabric with a value of 273 at a weight gain of 0.9% (0.017 D.S.).

EXAMPLE 3 A methanolic solution of the same composition as that shown in Example 1 was applied to a viscose rayon fabric, and the processing of the fabric was a duplication of the Example 1 operation. The wet pickup was 75%. Analysis of the finished fabric shows a crease angle (dry) value of 260 (W&F) at a weight gain of 2.9% (0.055). The untreated control shows a crease angle (dry) value of 213 (W&F), which indicates an increase of 22% in the treated fabric.

EXAMPLE 4 A methanolic solution of the same composition as that shown in Example 1 was applied to a ramie fabric,

EXAMPLE A rnethanolic solution of the same composition as that shown in Example 1 was applied to a dialdehyde cotton fabric, which was 6.9% oxidized by the periodate method, and had an aldehyde D8. of 0.14, and the wet pickup was 80%. The processing of the fabric was carried out as in Example 1. Analysis of the finished fabric shows a crease angle (dry) value of 268 at a 1.0% weight gain (0.019 D.S.). The untreated dialdehyde cotton (control) fabric shows a crease angle (dry) value of 203 (W&F). Thus the tested fabric shows an increase in dry recovery of 32% over the dialdehyde fabric, and 50% over the untreated cotton fabric.

EXAMPLE 6 A methanolic solution of the same composition as that shown in Example 1 was applied to a partially acetylated fabric (0.23 D.S.). The wet pickup was 90% and the processing of the fabric was carried out as in Example 1. Analysis of the finished fabric shows a crease angle (dry) value of 223 (W&F) at a 1.3% weight gain (0.025 D.S.). The untreated partially acetylated fabric shows a crease angle (dry) value of 155 (W&F), which indicates an increase of dry recovery for the tested fabric of 44% over the untreated partially acetylated fabric.

EXAMPLE 7 An isopropanolic solution of the same composition as that shown in Example 1 was applied to a cotton fabric of 80 x 80 count, and a 100% wet pickup was obtained. The processing of the fabric was carried out as in Example 1. Analysis of the finished fabric shows a crease angle (dry) value of 250 (W&F) at a weight gain of 1.4% (0.026 D.S.) Since the untreated cotton fabric had a 195 value, the improvement is an increase of 28.2%.

EXAMPLE 8 A catalytic reaction solution having the following composition was prepared:

Ingredient: Parts by weight dl Butadienediepoxide 20.0

Zinc fluoborate (40% aqueous solution) 1.5 Solution consisting of equal parts of water and dioxane 78.5

This solution was applied to 80 x 80 cotton fabric using a conventional padder and the wet pickup was 100%. The processing of the fabric was carried out as in Example 1. Analysis of the finished fabric shows a crease angle (dry) value of 251 (W&F) at a 2.2% weight gain (0.042 D.S.).

This entire operation was repeated using another piece of cotton fabric and a fresh solution in which the dioxane was replaced 'by water, and a 100% wet pickup was obtained. Analysis of this finished fabric shows a crease angle (dry) value of only 215 (W&F) at a weight gain of 0.7% (0.013 D.S.).

4 EXAMPLE 9 The procedure and ingredients of Example 1 were applied to a sample of cotton fabric of x 80 count and an wet pickup was obtained. The one variation, oven temperature, was C. Analysis of the finished fabric shows a crease angle (dry) value of 280 (W&F) at a Weight gain of 1.0% (0.019 D.S.).

EXAM i-LE 10 The same procedure and ingredients as in Example 9 were applied to another sample of cotton fabric, and a wet pickup of 85% was obtained. The one variation, oven temperature, was reduced to 85 C. The analysis of this finished fabric shows a crease angle (dry) value of 280 (Vi/81F) at a Weight gain of 1.0% (0.019 D.S.).

EXAMPLE 1 l The procedure and ingredients of Example 1 were applied to a carboxyrnethylated fabric of a degree of substitution of 0.1, and a wet pickup of 85% was obtained. Analysis of this finished fabric shows a crease angle (dry) value of 234 (W&F) at a weight gain of 2.2% (0.042 D.S.). The crease angle (dry) vaiue of the untreated carboxymethylated fabric was 173 (WSLF), therefore the improvement as shown by the increase was 37% over the value of the untreated carboxymethylated fabric.

We claim:

1. A process of imparting resiliency to a cellulosic textile material comprising:

(a) wetting a cellulosic textile material selected from the group consisting of cotton, viscose rayon, ramie, dialdehyde cotton, partially acetylated cotton, and carboxymethylated cotton with a solution containing about from 10 to 20 parts butadienediepoxide, 1.5 parts ZinC fiuoborate catalyst, and about from 78.5 to 88.5 parts of a solvent consisting of 50 parts by weight of dioxane and 50 parts by weight of water, and

(b) curing the wet cellulosic textile material at a temperature of about from 85 to C.

2. The process of claim 1 wherein the cellulosic textile material is cotton.

3. The process of claim 1 wherein the cellulosic textile material is viscose rayon.

4. The process of claim 1 wherein the cellulosic textile material is ramie.

5. The process of claim 1 wherein the cellulosic textile material is dialdehyde cotton.

6. The process of claim 1 wherein the cellulosic textile material is partially acetylated cotton.

'7. The process of claim 1 wherein the cellulosic textile material is carboxymethylated cotton.

References Cited UNITED STATES PATENTS 2,752,269 6/1956 Condo et al 8-116 X 3,150,920 9/1964 Berni et al. 8120 OTHER REFERENCES McKelvey et al. I: American Dyestuif Reporter, vol. 49, pp. 804-809 (1960).

McKelvey et al. II: Journal of Polymer Science, vol. 51, pp. 209-219, 223-228 (1961).

Benerito et al.: Textile Research Journal, vol. 31, pp. 757-769 (1961).

NORMAN G. TORCHIN, Primary Examiner.

J. CANNON, Assistant Examiner. 

1. A PROCESS OF IMPARTING RESILIENCY TO A CELLULOSIC TEXTILE MATERIAL COMPRISING: (A) WETTING A CELLULOSIC TEXTILE MATERIAL SELECTED FROM THE GROUP CONSISTING OF COTTON, VISCOSE RAYON, RAMIE, DIALDEHYDE COTTON, PARTIALLY ACETYLATED COTTON, AND CARBOXYMETHYLATED COTTON WITH A SOLUTION CONTAINING ABOUT FROM 1/ TO 20 PARTS BUTADIENEDIEPOXIDE, 1.5 PARTS ZINC FLUOBORATE CATALYST, AND ABOUT FROM 78.5 TO 88.5 PARTS OF A SOLVENT CONSISTING OF 50 PARTS BY WEIGHT OF DIOXANE AND 50 PARTS BY WEIGHT OF WATER, AND (B) CURING THE WET CELLULOSIC TEXTILE MATERIAL AT A TEMPERATURE OF ABOUT FROM 85* TO 125*C. 